DE3035357A1 - Thermoplastic aromatic polyester (carbonate) moulding compsns. - contg. ammonium or alkali salt(s), opt. halogenated phthalimide(s) and opt. PTFE - Google Patents

Abstract

Flame-resistant moulding compsns. contain, by wt., (A) 92-99.9 (92-99.98) esp. 97.5-99.8 parts thermoplastic aromatic polyesters or polyester-carbonates, derived from diphenols, iso- and/or terephthalic acid or their halogenated or 1-4C alkylated derivs., (B) 0.01-3 (0.01-3) esp. 0.1-1 parts of at least one ammonium or alkali salt of an inorganic or organic acid, (C) 0-3 (0.01-3) esp. 0.1-1 parts of at least one halogenated phthalimide having formula (I) or (II), (where R is H, 1-10C alkyl, Ph, naphthyl, C6H4X, C6H3X2 or C6H2X3; R' is a plain bond, 2-4C alkylene, phenylene or p-diphenylene; Z is Cl or Br) and (D) 0-2 (0-2) esp. 0-0.5 parts PTFE. The compsns. are used in shaped article prodn., esp. by injection moulding. Polyester- and polyester(carbonate) flame-proofing with (B), opt. (C) and (D), is achieved without reducing their mechanical and chemical properties. Flame-inhibiting activity of (B), opt. (C) and (D) corresponds to 6 times the wt. of decabromodiphenyl ether without the high lowering in notched impact tenacity.

Description

Flame-retardant molding compounds based on thermoplastic

aromatic polyesters and polyester carbonates, process for their Production and their use for producing molded articles The invention relates to flame-retardant molding compounds, the thermoplastic polyesters or polyester carbonates based on diphenols and iso- and / or merephthalic acids, and as flame retardants Containing ammonium or alkali salts of perfluoroalkanesulfonic acids, a process for the production of these molding compositions and their use for the production of moldings.

Aromatic polyesters are known (W.M. Eareckson, J. Polym. Sci. XL, 399-406 (1959); André Conix, "Thermoplastic Polyesters from Bisphenols", Ind. Closely.

Chem., Vol. 51, Wo. 2, 147-150, Feb. 1959; FR 1 177 517, US 3 351 624, DE-AS 1 445 384). They are used everywhere because of their excellent properties Used where high heat resistance and toughness are required.

Due to their high content of aromatic building blocks, they have molded parts from aromatic polyesters a favorable fire behavior: they are difficult to un- flames and burn, once ignited, continue slowly or extinguish by themselves. However, this fire behavior is sufficient for many applications not from.

A fire behavior VO according to the test standard of Underwriters' is desirable Laboratories, Subj. 94, hereinafter referred to as UL-94. According to this test standard Test specimens (rods with dimensions of 127 x 12 x 3.2 or 1.6 mm) after ignition do not drip off and have a maximum average afterburn time of 5 seconds.

The flame retardants used up to now are either a cause for reduced color stability of the melt or reduce the toughness or the Weather stability of the polycondensates is essential.

Surprisingly, it has now been found that ammonium and alkali salts of perfluoroalkanesulfonic acid in aromatic polyesters and polyester carbonates show the same flame-retardant effect as about six times the amount by weight of decabromodiphenyl ether, without the disadvantages described above occurring at the same time.

The invention relates to flame-retardant molding compositions containing a) 99 to 99.99, preferably 99.6 to 99.8, parts by weight of thermoplastic aromatic Polyester resp.

Polyester carbonates based on diphenols, isophthalic and / or terephthalic acid or their halogenated or C1-C4-alkylated derivatives and b) 0.01 to 1, preferably 0.1 to 0.4 parts by weight of at least one ammonium or Alkali salt of a perfluoroalkanesulfonic acid with 1 to 10, preferably 1 to 6, carbon atoms.

Another object of the invention is a method for production these molding compositions, after which components a), b) and optionally other auxiliaries - preferably in the melt - combined with one another.

The invention also relates to the use of these molding compositions for the production of moldings.

The aromatic polyesters and polyester carbonates a) can in addition to the residues of diphenols and iso- resp.

Terephthalic acids also include residues of monophenols, aromatic monocarboxylic acids and branching agents.

As a rule, they have relative solution viscosities from 1.18 to 2.0, preferably from 1.2 to 1.5 (measured in a solution of 0.5 g polyester in 100 ml dichloromethane solution at 250C).

Preferred diphenols for the production of the polyesters and polyester carbonates a) are compounds of the formula HO - A - OH (I) in which A is a divalent monovalent or polynuclear aromatic radical with 6-30 carbon atoms, where A like that is built that the two OH groups directly to one carbon atom of an aromatic System are bound.

Particularly preferred diphenols are compounds of the formula in which a single bond, an alkylene or alkylidec radical with 1-7 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 - 12 0 atoms, -O-, -S-, means, as well as their nucleus alkylated and nucleus halogenated derivatives, eg

Hydroquinone resorcinol, dihydroxidiphenyls, bis (hydroxiphenyl) alkanes, Bis (hydroxiphenyl) cycloalkanes, bis (hydroxiphenyl) sulfides, bis (hydroxiphenyl) ethers, Bis (hydroxiphenyl) ketones, bis (hydroxiphenyl) sulfoxides, bis (hydroxiphenyl) sulfones and α, α'-bis (hydroxiphenyl) diisopropylbenzenes as their ring-alkylated and ring-halogenated derivatives. These and other suitable ones Diphenols are e.g.

in U.S. Patents 3,028,365, 3,275,601, 3,148,172, 3,062,781, 2 991 273, 3 271 367, 2 999 835, 2 970 131 and 2 999 846, in the German Offenlegungsschriften 1 570 703, 2 063 050, 2 063 052, 2 211 956, 2 211 957, the French Patent specification 1 561 518 and in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York, 1964 ".

The most important diphenols are listed below by name: Bisphenol A = 2,2-bis- (4-hydroxiphenyl) -propane, tetramethylbisphenol A, 1,1-bis- (4-hydroxiphenyl) -isobutane, 1,1-bis (4-hydroxipnenyl) cyclohexane, 4,4 "-dihydroxidiphenyl sulfide, 4,4'-dihydroxidiphenyl, 4,4'-Dihydroxidiphenylsulfon and their di- and tetrahalogenated derivatives. Particularly bisphenol A is preferred.

Any mixtures of the aforementioned diphenols can also be used will.

As a chain terminator for aromatic polyesters and polyester carbonates a) can, for example, phenol, alkylphenols with C1-C12-alkyl groups, halogenated Phenols, hydroxidiphenyl, naphthols, chlorocarbonic acid esters from such phenolic Compounds and chlorides of aromatic monocarboxylic acids represented by C1-C12 alkyl groups and halogen atoms may be substituted.

As a branching agent for aromatic polyesters and polyester carbonates a) can, for example, 3 or higher functional carboxylic acid chlorides, such as trimesic acid trichloride, Cyanuric acid trichloride, 3,3 ', 4,4'-benzophenone-tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 to 1.0 mol% (based on used dicarboxylic acid derivatives) or 3- or higher-functional phenols, such as phloroglucinol, 4,6-dimethyl-2, 4, 6-tri- (4-hydroxiphenyl) -hepten-2 4,6-dimethyl-2,4,6-tri- (4-hydroxiphenyl) -heptane, 1,3,5-tri- (4-hydroxiphenyl) -benzene, 1,1,1-tri- (4-hydrosiphenyl) -ethane, tri- (4-hydroxiphenyl) -phenylmethane, 2, 2-bis / 4, 4-bis- (4-hydroxiphenyl) -cyclohexyl / -propane, 2,4-bis- (4-hydroxiphenyl-isopropyl) -phenol, Tetra- (4-4-hydroxiphenyl-isopropyl7-phenoxy) methane, 1,4-bis - / (4,4 "-dihydroxitriphenyl) methyl7-benzene can be used in amounts of 0.01 to 1.0 mol% (based on the diphenols used).

The aromatic polyesters can be prepared using the transesterification process (V.V. Korshak and S.V. Vinogradova in "Polyesters", Pergamon Press (1965), 449) or by Elimination of hydrogen chloride from the acid chlorides and the phenolic starting components in the melt, in solution or in the phase boundary process (DE-OS 27 14 544; V.V. Korshak and S.V. Vinogradova in "Polyesters", Pergamon Press (1965), 469) will Phenolic branching agents can be used with the diphenols Submitted, acid chloride branching agents can be used together with the acid chlorides be entered.

Also the aromatic polyester carbonates a) and processes for their Manufacture are known (G.S. Kolesnikow et al, J. Polym. Science USSR, Vol. 9, 1967, pp. 1705 to 1711; US 2,030,331, 3,169,121, 3,409,704, DE-OS 2,714,544, 2,758 030).

Aromatic polyester carbonates a) for the purposes of the invention can up to 90 mol%, preferably up to 45 mol, based on the sum of ester and carbonate groups, Contain carbonate groups.

Preferred ammonium and alkali salts b) are the ammonium, sodium or lithium salts, but especially the potassium salts of perfluoro-C1-C6-alkanesulfonic acids.

Particularly preferred ammonium and alkali salts b) are the sodium or potassium salts of perfluorobutanesulphonic acid and perfluoromethanesulphonic acid.

The molding compositions according to the invention can be used in addition to the flame retardants nor stabilizers, flow and mold release agents, plasticizers and fillers, such as glass fibers, glass spheres, asbestos or carbon fibers, kieselguhr, kaolin, Contains rock flour and pigments.

The flame retardant combinations are the aromatic polyesters and polyester carbonates wisely in the melt, for example in an extruder, if necessary together with auxiliaries, fillers and reinforcing materials.

The molding compositions according to the invention can by customary processes in Injection molding machines are processed into moldings or in extruders into semi-finished products.

Refer to the percentages given in the examples below unless otherwise stated, based on weight.

Examples A. Preparation of the polyesters and polyester carbonates.

Polyester 1: Manufacture of an aromatic polyester from bisphenol A and equimolar amounts of isophthalic acid chloride and terephthalic acid chloride in 7.52 kg 45-tiger sodium hydroxide solution and 160 l of water were 9.12 kg of bisphenol A, 24 g of sodium borohydride and 150.4 g Phenol (4 mol%, based on bisphenol A) dissolved under a nitrogen atmosphere. In 148.4 g (1 mol%) of triphenylethylphosphonium bromide were introduced into this solution and then 60 kg of dichloromethane and 48 kg of chlorobenzene were added.

Into the vigorously stirred two-phase mixture was cooled with water within 15 minutes at an internal temperature of 20-250C and at a pH value from 12 -13 a solution of 4141.2 g each of iso- and terephthalic acid dichloride in 12 1 Dichloromethane entered.

After the addition had ended, stirring was continued for 15 minutes, followed by the Separated alkaline-aqueous phase, the organic phase initially with dilute Phosphoric acid, then washed with water until the wash water has conductivity of 1 - 10 5 S / cm and the main amount of dichloromethane under normal pressure distilled off (bottom temperature up to approx. 100 ° C).

The remaining, still hot solution of the aromatic polyester 1 in Chlorobenzene was at 3200C in a vacuum twin screw extruder (screw diameter 32 mm) at approx. 0.014 bar down to a residual content of approx. 50 ppm freed from chlorobenzene, the aromatic polyester 1 is drawn off as a strand and granulated.

Polyester 2 Manufacture of an aromatic polyester from bisphenol A and isophthalic and terephthalic acid in a molar ratio of 3: 2 in 7.52 kg of 45% sodium hydroxide solution and 160 l of water were 9.12 kg of bisphenol A and 24 g of sodium borohydride under a nitrogen atmosphere solved. 91 g of triethylbenzylammonium chloride were introduced into this solution and then 60 kg of dichloromethane and 48 kg of chlorobenzene were added.

Into the vigorously stirred two-phase mixture was cooled with water within 15 minutes at an internal temperature of 20-25 "C and at a pH value from 12-13 a solution of 4968 g isophthalic acid dichloride, 3312 g terephthalic acid dichloride and 333 g of p-isooctylphenol entered in 12 l of dichloromethane. Further processing was carried out as described for polyester 1.

Polyester carbonate 3 Production of a polyester carbonate with 70 mol% Carbon ester content, statistically distributed, from bisphenol A and iso- and terephthalic acid chloride in a molar ratio of 1: 1 in a steel kettle with an intensely working stirrer under a nitrogen atmosphere 2.736 kg bisphenol A, 1.5 1 45% aqueous sodium hydroxide solution, 8.4 g sodium borohydride, 120 g triethylbenzylammonium chloride, 36 1 water, 11 1 dichloromethane and 11 1 chlorobenzene filled and the mixture up to complete solution of bisphenol A stirred.

The vigorously stirred two-phase mixture was then cooled with water within 15 minutes a solution of 852.72 g each of iso- and terephthalic acid chloride and 39.5 g (3.5 mol%, based on bisphenol A) phenol in 3 liters of dichloromethane and stirred for 1 hour. The temperature of the reaction mixture exceeded it not 220C.

The pH of the mixture was increased by adding sodium hydroxide 12-13 held.

With continued stirring, 600 g of phosgene were introduced, whereby the temperature was again kept at approx. 200C and the pH value at 12-13 After the introduction of the phosgene, 120 ml of a 4 own aqueous solution of Triethylamine was added and the mixture was stirred for a further 1 hour.

After the aqueous alkaline phase had been separated off, the organic phase became Phase washed free of salt first with dilute phosphoric acid, then with water and about 50% of the dichloromethane is distilled off under normal pressure. The remaining one The solution was diluted with 15 l of chlorobenzene, and the dichloromethane was distilled off continued until the sump temperature was about 800C, then the polyester carbonate 3 freed from chlorobenzene in a vacuum extruder at 3200C, drawn off as a strand and granulated. That Granules had a relative solution viscosity Irel of 1.262.

Polyester carbonate 4 Production of a polyester carbonate with 90 mol% Carbon ester portion in the form of blocks, from bisphenol A and iso- and terephthalic acid chloride in a molar ratio of 1: 1 As for polyester carbonate 3, 2.736 g of bisphenol A, 1.5 1 45 strength aqueous sodium hydroxide solution, 180 g of triethylbenzylammonium chloride, 8.4 g of sodium borohydride, 36 1 water, 11 1 dichloromethane and 11 1 chlorobenzene until completely dissolved of the bisphenol A stirred, then a solution into the mixture with vigorous stirring from 1096.38 g each of isophthalic acid chloride and terephthalic acid chloride and 67.86 g of p.-tert.-butylphenol (3.77 mol%, based on bisphenol A) in 3 liters of dichloromethane within 15 minutes registered. After stirring for 1 hour, 215 g phosgene initiated. The pH was the same as in the 1st stage of the reaction with sodium hydroxide at 12-13, the temperature kept below 220C by cooling. The post-reaction lasted 1 hour. In addition, no tertiary amine was used as a catalyst used. After the work-up described for polyester carbonate 3, the relative solution viscosity of the granules obtained 1.248.

In the polyester 1-2 and the polyester 3-4 were in one Twin screw extruder (screw knife 32 mm) at approx. 3200C in each case 0.2 wt .-% potassium perfluorobutanesulfonate incorporated, from the obtained Mixtures of test bars measuring 127 x 12.7 x 1.6 mm (1/16 inch) and 127 x 12.7 x 3.2 mm (1/8 inch) injection molded.

The fire behavior according to UL, Subj. 94, checked. An Allocation of the materials to the following 3 flammability classes (flame exposure 10 sec each): Flammability class UL 94 V-O The individual test specimens burn a maximum of 10 seconds, the whole set of 10 bars together a maximum of 50 seconds. If If molten material drips off the burning stick, it does not ignite the wadding.

UL 94 V-1 The individual test specimens burn for a maximum of 30 seconds, the whole Set of 10 sticks together for a maximum of 250 seconds. Otherwise as with 94 V-O.

UL 94 V-2 afterburn times as with 94 V-1, dripping molten However, material may ignite the wadding.

All resins and both rod thicknesses gave fire behavior V-O.

Claims (7)

Claims: (1. Fla = mwidely molding compositions containing a) 99 to 99.99 parts by weight of thermoplastic aromatic polyesters or polyester carbonates based on diphenols, iso- and / or terephthalic acid or their halogenated respectively. C1-C4-alkylated derivatives and b) 0.1 to 1 part by weight at least of an ammonium or alkali metal salt of a perfluoroalkanesulfonic acid with 1 to 10 carbon atoms. 2. Molding compositions according to claim 1, characterized in that they are 99.6 up to 99.9 parts by weight a) and 0.1 to 0.4 parts by weight b). 3. Molding compositions according to Claims 1 and 2, characterized in that the ammonium or alkali salts contain 1 to 6 carbon atoms. 4. Molding compositions according to claims 1-3, characterized in that the Component b) is potassium perfluorobutane or methanesulfonate. 5. Molding compositions according to claims 1-4, characterized in that component a) a relative solution viscosity of 1.18 to 2.0 (measured in a solution of 0.5 g polyester in 100 ml dichloromethane solution at 25 ° C). 6. Process for the production of the molding compositions according to Claims 1-5, characterized in that characterized in that components a), b) and optionally other auxiliaries - preferably in the melt - united with one another. 7. Use of the molding compositions according to claims 1-5 for the production of Moldings, especially injection molded articles.